Composition and drying of the same



Nov. 30, 1937. w. J. KOENIG 2100,484

COMPOSITION AND DRYING OF THE SAME Fiied Feb, 23, 1935 2 Sheets-Sheet l FIG-1 VAPOR PRESSURE uv m1. mencunv TEMPERATURE DEG. CENTIGHRDE FIG-2 VAPOR PRESSURE IN MM MERCURY TEMPERATURE 05g. CENTIGFMDE INVENTOH WALTER I AOE/V/G Nov. 30, 1937. w. J. KOENIG 2,100,484

COMPOSITION AND DRYING ,OF THE SAME Filed Feb. 23, 1955 2 Sheets-Sheet 2 VAPOR PRESSURE rm. MERCURY 40 40 80 loo -120' vl'EI*'HERI\TIlRE-- DEG- CENT INVEN TOR wan-Er? J- KOEN/G 1 ATTORNEY a n Nov.30,1937

, coMrosrrroN AND DRYING or win; SAME Walter J. Koenig,.-Trenton,

rporation, corporation of Delaware Sloane-Blabon N. J., assignor to Trenton, N. J., a

Application February 23,1935, Serial No. 7,717

-7 Claims. (01-91-70) This invention relates to a drying'oil composition and to method of drying oils. More particu-' larly the invention relates to a composition and method in which surface distortion isprevented 5 by protecting the surface of the oil against excessively rapid oxidation and especially by evapcrating a non-oxidizing. slowly volatile substance from said surface.

Certain oils, and' especially China-wood oil, which possess extremely valuable properties in other respects, are subject to the great disadvantage that on drying tend to surface distortion thereby producing wrinkled and/or orange peel effects. These features-are undesirable particue x5 larly when a smooth surface is desired, as, for example, in printed materials in the linoleum and felt base industry, or in anyplace where enamels, paints, varnishes, etc., using drying-oils hereinaftr discussed, are used on a surface.

An additional disadvantage of the above described oils is-the tendency of these oils to skin" over or to harden while awaiting use.

- It is, therefore, an object of my present invention to prevent or substantially reduce the tendency of such oils from wrinkling and/or orangev peeling during the drying of the oils. An additional object is to substantially reduce the skinning-over tendency of paints or similar coating compositions in which such oils are used as vehicles. v

I have found, through the medium of my invention hereinafter dwcribed, that surface distortion can beprevented orcontrolled and that even withvery rapid drying at superatmospheric smooth and substantially perfect temperatures.

films can be obtained if the surface .of the film is protected from excessively rapid oxidation during the drying action. It is necessary that the dryins p o 40 the film while the surface of the film is protected from oxidation: through, the medium of a protesting non-oxidizing gaseous blanket at the interface of the surface to be dried and the atmosphere.

atmosphere. was method tially uniformly throughoutgroups enumerated in able. It is understood, however, that smooth films can be obtained by this method.

, Due to the difficulties involved in the method described, I have found that it is more desirable to control the atmosphere immediately'above the 5 urface of the dryingoilfilm by incorporating the protective substance in the film itself. If, for

example, a non-oxidizing evaporating material is incorporated in the oil composition film to be dried, so that its vapors are given off from the 10 surface during 'the drying period at super-atmospheric temperatures, a practical protection is secured and smooth films, either, glossy or matte finishes, are readily obtained. It-is, of course, desirable to avoid rapid circulation of'thegasesi 15 the gases in the chamber should be substantially stagnant. The protective agents or substances which are incorporated directly with the drying oil may be either reactive or non-reactive with the oil. I

have found that'in order to reduce costs in pro- .duction, and at the same time reduce complications in the process, it is preferable to'use substances which will condense with the drying oil and the uncondensed excess portion, on being volatilized, will form the protective layer above thefilmtobedried.

I In considering reactivessubstances which will condense with the drying oil, as described in-my co-pending application No. 646,148, filed. Decemso her 7, 1932, of which the present application-is a continuation in part, the condensing agent is I supplied in excess and the uncondensed" portion on volatilizing. Preferably at super-atmospheric temperatures, will form the desired protective .blanket. For example, in the preferred examples 35 'of application No. 646,148, the cyclohexanol and cyclohexanone were supplied in excess, and the evaporation of these substances from the surface during the drying action at super-atmospheric temperatures served to protect thesurface against rapid oxidation and thus to perinit the drying to proceed by the condensation reaction in the film before oxidation had dried the surface. 5 v l The reactive substances'particularly desirable in the present invention may be chosen from the y co-pendins snplications, Serial Nos. 646,148,1lled December 7, 1932; 758,859; 758,860: 758,861; 758,862; 758,863: 758,864, filed December. 22, 1934. Several examples are: cyclohexanol, cyclohexanone, phthalic' anhydride, di-acetone alcohol, furfuraldehyde, 'qulnone, fenchyl alcohol, fenchone, carvone, Inthe co-pendingapplications, the PM!!! u of improving the drying properties. of drying oils having double has been described and claimed. The drying reaction is improved through the medium of a condensation reaction wherein the oil condenses with organic compounds enumerated in the various applications. Through the medium of the condensation reaction, the hardening of the film will proceed uniformly throughout the thickness -of the film in contrast to the conventional hardening of oil films through oxidation. In drying films through oxidation, the surface of the film will harden first and the interior of the film tends to remain plastic. Through the medium of the hardening action of 011 films, as described in the above indicated co-pending applications, in which the hardening proceeds uniformly throughout the thickness of the film, more flexible and better wearing films are acquired. It has been shown that the uniform hardening action proceeds especially in non-oxidizing atmospheres created by the slow evaporation of the volatile organic substances mixed with the oil prior to the spreading of the oil into films. If the hardening reaction is carried on'in oxidizing atmospheres, the hardened film has a dull matte finish in contrast to the desirable gloss finish obtained in non-oxidizing atmospheres.

Non-reactive substances, that is, substances which will not condense with the oil when added to the drying oil, will, on being evaporated therefrom at super-atmospheric temperatures, form a protective blanket exactly as is formed in the case of the reactive substances discussed above. For example, substances such as,hydroterpene, hydrogenated naphthalene, kerosene, cymene, etc., do not condense with the drying oil when treated under circumstances described in my copending applications, but will, on being evaporated from the oil, form a protective blanket over the film and thereby prevent surface oxidation.

Also, generally accepted anti-oxidants which may be reactive or non-reactive with the oil such as, thymol, hydroquinone, phenol, guaiacol, re-- sorcinal, pyrogallol; glycollic acid, furfuraldehyde, furfural, benzoic and salicyclic acid, ornaphthylamine, diphenylamine, phenyldimethylamine, diphenylguanidine, diphenylhydrazine, onitroaniline, p-naphthol, a-terpineol, which have relatively high vapor pressures, will, on being added to the drying oil and then evaporated from the oil at super-atmospheric temperatures, form the protective blanket above the oil film as heretofore described. It is interesting to note with respect to anti-oxidants of oxy-compounds, classified as anti-oxidants, are reactive condensing agents with drying oils such as, China-wood oil and oils of similar structure. Similarly, as in the case of reactive sub stances, when a reactive anti-oxidant substance is added to the drying oil, an excess is added and the portion, which does not enter the condensation reaction with the drying oil, will form the protective blanket when evaporated from the oil. If a non-reactive anti-oxidant is added to the drying oil, the substance will form a protective gaseous blanket over the drying oil when the drying action is caused to proceed at superatmospheric temperatures.

In cases where non-reactive substances are used in the drying oil in the absence of condensing agents, as described above,,the drying of the oil proceeds by polymerization when the temperature is raised to super-atmospheric conditions and the non-reactive substance merely creates bonds in conjugate arrangement face distortion, are used, it is that a large percentage the non-oxidizing protective blanket over the oil during the drying action.

As previously indicated, I prefer to use reactive substances, which, on being added to the oil in excess quantities, a portion will conden'se with the oil and the remainder will form the protectiveblanket as it is evaporated from the drying film. If only a sufllcient quantity of reactive condensing agents is added to the drying oil to cause the condensation product to form with the oil as described in co-pending cases, a quantity of a non-reactive substance may be added to the oil to form the protective blanket. The non-reactive substance will, in this case, on being volatilized during the drying action at super-atmospheric temperatures, blanket.

In general, any substance which is non-oxidizing and which, when added to the drying oil in amounts up to twenty-five percent, based on the oil, will give a mixture having, between 104 F. and 212 F., vapor pressures between 2 mm. and mm. column of mercury may be used. Those substances which have the lower vapor pressure ranges within the temperature range are the more desirable, and I have found, for example, that those falling within the range between 2 mm. and 60 mm. and especially those formed between 2 mm. and 50 mm. produce much better results than those extending into the higher range specified. When driers, which hasten the drying action, but ordinarily aggravate wrinkling and surdesirable, in order to prevent or minimize wrinkling or other surface distortion, to use as protective agents those materials whose vapor pressures 'within the temperature range, do not exceed approximately 25 mm.

As one example of according to my invention, suggested:

A vehicle may be made by hot blending the following ingredients:

the use of such materials the following may be Parts by weight The procedure of blending, which I prefer, is to place the above mixture in a.-Bedford kettle and blow at 200 F. or reflux at the boiling point of the mixture until it attains a desired viscosity. It is then cooled to room temperature; This forms a vehicle to which pigments and fillers may be added in the conventional manner.

When it is desired to dry the prepared mixture, the mixture is spread out in a closed chamber and heated to about F. The unreacted cyclohexanol will evaporate, forming the protective film over the surface of the mixture, and

help to form the protective the drying of the oil mixture continues until I made, as folbodied China-wood oil, and the hydroterpene. 75

It is then cooled and the resulting vehicle may be mixed with pigments and fillers in the conventional manner. As in the previous example,

the resulting mixture is spread out in a closed chamber and the temperature is raised to about 140 F. The evaporating hydroterpene will form the desired protective non-oxidizing blanket as the mixture dries to a smooth film.

In the accompanying drawings I have shown graphs of the vapor pressures of the China-wood oil mixtures within the temperature range specified for each of various protective materials.

Throughout the application, the term. 7".

blown China-wood oil refers to China-wood oil blown to a '7 second viscosity as determined by the Gardiner-Holt tube at 86 F.

In Figure 1 are shown for comparison graphs for 7" blown'China-woo'd oils alone.

In Figure 2 are shown graphs of a group of materials which serve both as condensing agents and as protective agents.

In Figure 3 are shown graphs of agroup-of non-reactive protective agents.

On these figures the graphs represent the following materials A7" blown China wood oil after heating for one hour at'95 to 97-" C.

3-7" blown China wood oil untreated.

C-'7" blown China wood oil and 10% indene.

'D 7" blown China woodoil and 10% cyclo hexanol. r E-I' blown China wood oil and 10% furiural. F-7" blown China wood oil and 10% phenol. G7" blown China wood oil and 10% terpineol. i 3 I-I7" blown China wood oil and 10% butyl acetate. I7" blown China wood oiland 10% ethylene glycol mono butyl ether.

J-7" blown China wood oil .and 10% D-menthane. K7" blown China wood oil and 10% kerosene. L-7" blown China wood oil and 10% saturated naphthalene.

M-7" blown China wood oil and 10%-naphthalene.

N blown China wood oil and 10% phenylether. blown China wood oil and 10% o-nitro toluene. In the above'I have discussed particularly the application of my invention to China wood oil. Because of the valuable propertiesof China wood oil which are generally recognized in the art, thegreatest value of my invention at the presenttime will, undoubtedly, be in connection with the drying of China wood oil. It is to be under: stood, however, that my invention is nonethe less applicable to other oils which exhibit a tendency to surface distortion during drying.

The accompanying graphs disclose mixtures in which the volatile organic substances are 10% of the mixtures; however, excellent results have been obtained with mixtures in which the volatile organic substancewaspresent in amounts up to 2 of the mixture. The disclosure of the quantity of volatile organic substance added in the examples and-preceding statement shall not be construed asiiimiting the scope of the claims, since, if the rapidity is not of importance, the quantity of the organic substance can be varied in broad limits. If the quantity of the volatile organic substance added linseed 011-,

drying conditions, especially drying, whereas with from the filmsurface of the hardening of the film'- to the mixture exceeds 25% of the mixture, the

rapidity of the hardening action of the film is decreased.

Oils which exhibit a tendency to surface distortion during drying, but which can readily be driedwith smooth and undistorted films in accord with my invention, include treated and un-' treated drying oils, treated semi-drying oils and non-drying oilsthat possess double bonds in conjugate arrangement, e. g., C=CC=C- or -C=CC=C-C=C, (such as-China wood oil, fish oils, oiticica oil, blown or properly oxidized bean oil, blown or properlyoxidized poppyseed oil, etc., castor oil heated under reduced pressures to form conjugate double bond structure and esterified, blown or properly oxidized drying oil fatty acids, and the above treated and untreated oils, having the above double bond conjugate structure, blown with drying oil fatty acids or such oils to which blown or properly oxidized fatty acids have been added), fall'within thescope of my invention. Y

As already stated, driers may be used in compositions embodying the .present invention, but their use is not necessary; with the highly reactive oils with which we and should, in general, be avoided. Where driers are used, the difiiculty of preventing wrinkling I have found that especially good results are achieved by using a condensing agent as the slow evaporating protective agent.

Although I have set forth above in detail sev-.

eral specific examples and various alternatives and modifications thereof, it is tobe understood that these are given only for purposes of'illu's tration and that numerous changes which will be evident to those skilled in the art may be made a without departing from the scope of my invention.'.

i What I claim is: a I

1.-In the treatment and hardening of an oxidized ,oil, having double bonds in conjugate arrangemenhthef steps-which comprise adding reactive volatile organic substance to the oil in excess whereby a film-forming mixture includblown or properly oxidized soya are especially concerned,

ing unreacted volatile organic substance is formed, then spreading the mixture, into films on a supporting base and heating the spread mix-' ture to elevated temperatures, sufficient-to simultaneously slowly evaporate the remaining volathe constituents of the film-fo'rmingmixture forminga gaseous protecfilm, and substantially-exfrom contacting the film tive'blanket over the clude oxidizing gases and sumc'ientto cause a substantially non-oxidizing hardening of the o 2. In the treatment and hardening of an oxidlzedoil having double bonds in conjugate arrangement, as defined in claim 1, in which the oil is China wo'od oil.

3. In the treatmentandhardeningof'an'oxidlzed oil. having double bonds in conjugate arrangement, the stepswhich comprise adding reas mixture with said oil will give a range of vapor active and non-reactive volatile organic substances to the oil whereby, a film-forming mixture is formed, then spreading the mixture into films on a supporting base and heatingthe spread mixture to elevated temperatures, sufilcient to simultaneously slowly evaporate the remaining.

volatile constituents of the film-forming mixture from the film surface forming a gaseous protective blanket over the film and substantially exclude oxidizing gases from contacting the film and sumcient to cause a substantially non-oxidizing hardening of the oil.

4. In the treatment and hardening of an oxidized oil having double bonds in conjugate ar-- cient to simultaneously slowlyevaporate the remaining volatile constituents of the film-forming mixture from the film surface forming a gaseous protective blanket over the film and substantially exclude oxidizing gases from contacting the film and sufficient to cause a substantially non-oxidizing hardening of the oil.

5. In the treatment and hardening of an oxidized oil having double bonds in conjugate arrangement, the steps which comprise adding reactive volatile organic substance, of which a 10% pressures between two and twenty-five mm. mercury column at temperatures between 104 and 212 F., to the oil in excess whereby a film-forming mixture including unreacted volatile organic substance is formed, then spreading the mixture into films on a supporting base and heating the spread mixture to elevated temperatures, suflicient to simultaneously slowly evaporate the remaining volatile constituents of the film-forming mixture from the film surface forming a gaseous protective blanket over the film and substantially exclude oxidizing gases from contacting the film and sufllcient to cause a substantially non-oxidizing hardening of the oil.

6. In the treatment and hardening oi.v an oxidized oil having double bonds in conjugate arrangement, the steps which comprise adding to the oil in excess of the amount necessary to react with the oil a reactive volatile organic substance in amounts up to 25 percent of the mixture, of which a 10 percent mixture with said oil will give a range of vapor pressures between two and sixty mm. mercury column at temperatures between 104 and 212 F., whereby a filmforming mixture including unreacted volatile organic substance is formed, then spreading the mixture into films on a supporting base and heating the spread mixture to elevated temperatures, sufilcient to simultaneously slowly evaporate the remaining volatile constituents of the film-forming mixture from the film surface forming a gaseous protective blanket over the film and substantially exclude oxidizing gases from contacting the film and suificient to cause a substantially non-oxidizing hardening of the oil.

7. In the treatment and hardening of an oxidized oil having double bonds in conjugate arrangement, the steps which comprise adding to the oil in excess of the amount necessary to react with the oil a'reactive volatile organic substance in amounts up to 25 percent of the mix-' ture of which a 10 percent mixture with said oil will give 'a range of vapor pressures between two and twenty-five mm. mercury column at temperatures between 104 and 212 F., whereby a film-forming mixture including unreacted volatile organic substance is formed, their spreading the mixture into films on a supporting base and heating the spread mixture to elevated temperatures, sufiicient to simultaneously slowly evaporate the remaining volatile constituents of the film-forming mixture from the film surface forming a gaseousprotective blanket over the film and substantially exclude oxidizing gases from contacting the film and'suflicient to cause a substantially non-oxidizing hardening of the oil.

WALTER; J. KOENIG. 

